DE239211C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

- Me 239211 CLASS 22 h. GROUP

The condensation of o-halogen-substituted aminoanthraquinones with amirioanthraquinones available o-aminodianthraquinonylamines can easily be converted into dyes by oxidation, which apparently arise through the escape of two hydrogen atoms and ring closure and therefore belong to the type of anthraquinone hydroazines. The reaction is symbolized by the following scheme ίο:

> A '+ H ₂ O

NRH

Here ^ t and A ' mean any substituted or unsubstituted anthraquinone radicals (although an ortho division to the iViT group must be free for A' ), while R is hydrogen, an acyl radical or an alkyl

ao or aryl radical.

The oxidation can be effected in a variety of ways, e.g. B. in more concentrated Sulfuric acid with manganese dioxide or other similarly acting oxidizing agents or also by concentrated or fuming sulfuric acid alone. Furthermore, the oxidation can be achieved by heating with alkalis or phenolates. Also can the same goal can be achieved by heating with nitro bodies with or without additives an oxygen carrier. Finally, oxidation can also be achieved by mere heating to achieve a higher temperature with air admission, whereby the representation of the Aminodianthraquinonylamine and its further oxidation combined in a single operation can be.

It should also be noted that, under certain circumstances, further oxidation of the hydroazine formed to the corresponding azine can take place. One can thus obtain a varied number of dyes of the anthraquinone hydroazine series represent, many of which, such as B. the asymmetrically substituted, on other Paths were previously inaccessible.

Example 1.

In a solution prepared from 300 parts of phenol and 100 parts of potassium hydroxide, parts of o-Amino-a-ß-dianthrimid be entered at 140 to 150 ° and the 30 mixture while stirring gradually heated to 190 to 200 ^0th The thin, dark brown-black colored melt becomes viscous after about half an hour of heating. To end the reaction, it is expedient to hold at this temperature for a further hour. The mixture is then allowed to cool to about 140 ° to 150 ° and the melt is carefully diluted with water, the indanthrene formed separating out in crystallized form. The same is filtered, washed and dried.

Example 2.

30 parts of o-amino-α-β-dianthrimide are introduced into 600 parts of oleum containing 80 percent SO _{3 at ordinary temperature and dissolved with stirring.} The conversion into the azine of indanthrene takes place very quickly and is usually complete in 2 to 3 hours.

To isolate the reaction product, the melt is first mixed with 1200 parts of sulfuric acid from 60 ° Be. diluted, whereby one takes care by cooling that the temperature door Does not exceed 40 to 50 °, and then poured into water acidified with bisulfite. When the mixture is heated to 50 to 60 °, the azine changes into the indanthrene, the same thing is filtered, washed and dried. . . ·

Example 3.

25 parts of o-methylamino-a-ß-dianthrimide will be registered in 250 parts of anhydrous nitrobenzene and with 15 parts of dehydrated sodium acetate heated to boiling temperature for about 2 hours. The red melt gradually turns green-blue, separating when it cools blue colored needles made of methylindanthrene (see French patent 418908), which are isolated in a known manner by filtering, washing and drying.

Example 4.

5 parts of i-methylamino-2-bromoanthraquinone and 4 parts of 1 · 4-aminooxyanthraquinone are introduced into 100 parts of molten naphthalene and heated to boiling temperature ^{with 5 parts of dehydrated sodium acetate and 0.2 parts of copper dust with stirring for 2 1} _{hours for 2 to 3 hours.} After formation of the oxyo-methylamino-a-ß-dianthrimide has taken place, 10 to 20 parts of nitrobenzene are added to the violet-colored melt and kept at the boiling point until no more anthrimide can be detected. At the end the melt has a greenish blue color; part of the condensation product has already precipitated in the form of blue-colored crystal needles. To completely isolate the oxyfnethylindanthrene, the melt is diluted with crude pyridine while it is still hot and allowed to cool to about 70 to 80 °, then nitrated, washed out and dried.

The oxymethylindanthrene dissolves itself in high-boiling organic solvents, z. B. quinoline, extremely heavy with a blue-green color, in concentrated sulfuric acid green, blue flakes are precipitated out of this by water. By reduction with hydrosulfite and Caustic soda creates a brownish-yellow colored vat, which cotton has a greenish tinge stains blue tones.

Example.

15 parts of o-amino-a-ß-dianthrimide are dissolved in 300 parts of oleum (15 percent SO ₃ ) and stirred at 10 to 20 ° with a mixture of 10 parts of manganese dioxide in 100 parts of monohydrate. The melt, which was initially blue in color, gradually turns brownish-yellow. After the reaction has ended, the melt is poured into water mixed with bisulfite, the mixture is heated to the boil and the indanthrene which has separated out is filtered off, washed out and dried and any adhering impurities are removed by recrystallization from sulfuric acid.

Claims (1)

Patent claim: Process for the preparation of vat dyes of the anthracene series. consisting of that one treats o-aminoanthrimides with oxidizing agents.